Ionic liquids composed of phosphonium cations and organophosphate, carboxylate, and sulfonate anions as lubricant antiwear additives

Oil-soluble phosphonium-based ionic liquids (ILs) have recently been reported as potential ashless lubricant additives. This study is to expand the IL chemistry envelope and to achieve fundamental correlations between the ion structures and ILs physiochemical and tribological properties. Here we present eight ILs containing two different phosphonium cations and seven different anions from three groups: organophosphate, carboxylate, and sulfonate. The oil solubility of ILs seems largely governed by the IL molecule size and structure complexity. When used as oil additives, the ranking of effectiveness in wear protection for the anions are organophosphate > carboxylate > sulfonate. All selected ILs outperformed a commercial ashless antiwear additive. Surface characterization from the top and the cross-section revealed the nanostructures and compositions of the tribo-films formed by the ILs. Some fundamental insights were achieved: branched and long alkyls improve the ILs oil solubility, anions of a phosphonium-phosphate IL contribute most phosphorus in the tribo-film, and carboxylate anions, though free of P, S, N, or halogen, can promote the formation of an antiwear tribo-film.